Production of valuable hydrocarbons



Patented July 19, 1932 UNITED STATES PATENT; OFFICE;

rmz am) we EAEUBEB, or LnnwIosnArnN-oN-rnn-nnm, Gunman?) ABBIGNORS -TO I. G. FABBENINDUSTRIE AKTIENGESELLSCHAFT, OF FRANKFURT- ON-m-m, GERMANY, A CORPORATION OF GERMANY PRODUCTION OF V ALUAIBLE HYDROCARBONS Io Drawing. Application filed December 87, 1928, Serial No. 328,849, and in Germany January .5, 1888.

This invention relates to improvements in the manufacture and production of valuable hydrocarbons, especially those of liquid nature, althou h the production of gaseous hydrocarbons, ior example diolefines, such as bllitadiene or its homologues is also contemp ated. t

It is already known that hydrocarbons of higher molecular weight than that of the initial material can be produced by heating mixtures comprisin olefines and acetylene; for example, it is own-that, inter alia, butadiene can be obtained by heating a mixture of ethylene and acetylene in a lass retort to such a temperature that the said retort is brought to redness. But glass, quartz, porcelain, iron, nickel, copper, silver and many other materials suitable for the apparatus used in this reaction, cause extensive deposition of carbon and for this reason it has not hitherto been possible to carry out the processon a technical scale, because this is only practicable when the deposition of carbon is prevented.

We have now found that the said conversion ofolefines, such as ethyleneor propylene f together with acetylene can be carried out at high temperatures and without deposition of carbon if care be taken that the heated sees and vapors come into contact only with ree elements of grou 4 of the periodic system, such, for examp e, as tin silicon, lead,-

carbon in the form of graphite, or with zinc or aluminium or alloys containing substantial amounts of these metals. With this object in view it is essential that such hot portions of the conversion apparatus as come into contact with the gases and vapors should be constructed of the said metals or alloys or should be coated with them. The operation can also be conducted by simply passing the mixtures of olefines and acetylene under treatment through a highly heated bath of molten tin, zinc, lead, aluminium, or alloys of these metals with one another or withother metals which do not cause deposition of carbon, or with silicon or graphitic carbon.

The process may be carried on under elevated, atmospheric or diminished pressure. Usually pressure of up to about 50 or '100 atmospheres are employed, but, if desired,

higher pressures, for example 200 atmospheres or more, may also be employed. The reaction is usually carried out between about. 200 and 800 C. and preferably between about 300 and 600 C.

The materials hereinbefore specified not only prevent the deposition of carbon, but

also to a large extent exert a catalytic action. It is therefore advantageous to dispose them,

for example, on plates, in the reaction chamber.

It has also been found that the operation may be carried on in the presence of catalytic substances having a condensing action other than those hereinbefore specified. Anhydrous chlorides of the heavy metals, such as v "be in excess, and, if desired, the mixture may be diluted with one or more extraneous gases, or example nitrogen, methane or ethane, carbon dioxide or carbon monoxide. I

The latter method of operating may also be carried on under elevated or diminished pressure.

The following examples will further illustrate the nature of the saidinvention, but the invention is not restricted to these examples. The parts are by weight.

Example '1 v A mixture of equal parts of ethylene and acetylene is passed, from above downwards,

' per cent of methane. It can manganese also be conducted under elevated pressure.

Example 2 370 to 400 C., the reaction commences whereupon the same temperature is maintained for about 6 hours. On cooling, 72 per cent by weight of the mixture of ethylene and acetylene employed is recovered in the form of oil, of which 10 per cent, consisting mainly of butylene, boils below ordinary temperature, per cent, consisting mainly of benzene and toluene, boils up to 120 (1, and the rest boils up to 150 C. The catalyst remains perfectly free from tar or carbon.

Example 3 A mixture of 9 parts of ethylene and 1 part of acetylene is passed, at the rate of 10 liters per hour, through a manganese-copper tube coated internally with tin, 18 millimeters in diameter, which is heated over a length of 60' centimeters to about 600 C. 4' per cent of the transmitted gases is continuously converted, and the tube does not show the slightest deposition of carbon, even after prolonged use.

The condensate obtained on cooling to low temperatures contains 13 per cent of butadione, which'can be readily identified in the form of tetrabromide by adding on bromine. A further 7 per cent of the converted materials boils'below ordinary temperatures and the remainder boils up to about C. The residual gas contains ethylene, acetylene, a little propylene and butylene, and also 0.5 be employed for the process again after the addition of acetylene, which is the chief constituent consumed.

E'wample J;

The same conversion as described in Example 3 is carried on in a manganese copper tube coated internally with zinc. 5.5 per cent of the gas is converted into a liquid which boils, for the most part at between about 60 C. and 80 0., and consists almost entirely of benzene. Merely traces of buta diene can be detected in the conversion mixture, and only traces of methane are. present in the residual gas. No deposit of carbon can be found in the-tube itself after being in use for 120 hours. Benzene is also obtained as the chief product by-operating, in a similar way, at about 600 C., with a brass tube.

The tube may be replaced, for example, by an electrically heated tinned radiator of copper wire. The operation may 60 per cent carbons by heating a lead, tin, zinc,

Tin, zinc and the like have also proved very advantageous for internally coating the apparatus, in cases, where gases obtained b pyrogenic decomposition of tars, oils, b minous coals and the like and which contain olefines and acetylene, for example, 20-to 40 the ituper cent of the former and about 1 to 2 per cent of the latter, are subjected to the aforesaid treatment, since the said metals prevent the deposition of carbon. What we claim is 2- 1. In the production of valuable hydroolefine and acetylene, the step of brmgmg the said initial materials, while in the hot state, only into contact with substances selected from the class consisting .of carbon, silicon,

lead, tin, zinc, aluminium and alloys containing substantial amounts of these metals.

2. In theproduction of valuable hydrocarbons b heating a mixture comprising an olefine an acetylene, the step of bringing the said initial materials, only into contact with substances selected from theclass consisting of carbon, silicon, lead, tin, zinc, aluminium and alloys containing substantial amounts of these metals, and

- maintaining a temperature of between about 200 and 800 C.

3. In the production of valuable hydrocarbons by heating a mixture comprising an olefine and acetylene, the step of bringing the said initial materials while in the hot state,

only into contact with substances selectedfrom the class consisting of carbon, silicon,

lead, tin, zinc, ing substantial amounts of these metals, and maintaining a, temperature of between about 300and 600 C.

4. In the production of valuable hydrocarbons by heating a mixture com rising an olemixture comprising an while in the hot state,

aluminium and alloys containfine and acetylene, the step 0 bringing the y said initial materials, while in the hot state, only into contact with substances selec from the class consisting of carbon, silicon, aluminium and ing-substantial amounts of these metals, and maintaining an elevated pressure.

5. In thevproduction of valuable hydrocarbons by heating a mixture com risingan olefine and acetylene, the step 0 bringing the said initial materials, while in the hot state, only into contact with substances se-' lected from the class consisting of carbon, silicon, lead, tin, zinc, aluminium and alloys containing substantial amounts of in dilution with an extraneous as.

6. In the production of vauable hydro-' from the class consisting of carbon, silicon,

.lead, tin, zinc, aluminium and alloys containno. alloys containthese metals, andemploying the initial m xture:

ing substantial amounts of these metals, and treating the said mixture with a catalyst comprising an anhydrous'metal chloride.

7. In the production of valuable hydrocarbons by heating a mixture com rising an olefine and acetylene, the step 0 bringing the said initial materials, while in the hot state, only into contact with substances selected from the class consisting of carbon, silicon,

lead, tin, zinc, aluminum and alloys containing substantial amounts of these metals, and treating the said mixture with a catalyst comprising aluminum chloride.

8. In the production of valuable hydrocarbons by heating a mixture comprising an olefine and acetylene, the step of bringing a mixture comprising ethylene and acetylene, while in the hot state, only into contact with substances selected from the class consisting of carbon, silicon, lead, tin, zinc, aluminium and alloys containing substantial amounts of these metals.

9. In the production of valuable hydrocarbons by heatin a mixture comprising an olefine and acety ene, the step of bringing a mixture comprising ethylene and acetylene, while in the hot state, only into contact with substances selected from the class consisting of carbon, silicon, lead, tin, zinc, aluminium and alloys containing substantial amounts of these metals, and malntaining a temperature of between about 300 and 600 C.

10. A process for the production ofvaluable hydrocarbons which comprises passing a mixture comprismg ethylene and acet lene through a tube coated internally wit tin and heatedto about 600 C.

In testimony whereof we have hereunto set our hands. V

FRITZ WINKLER. HANS HA EUBER. 

